Polyvinyl butyral composition



. ucts with polyvinyl acetal resins.

Patented Nov. 9, 1948 I POLYVINYL BUTYRAL COMPOSITION Richard D. Dunlop, Longmeadow, Masa, assignor to Monsanto Chemical Company, St. Louis, Mo.,' a corporation of Delaware No Drawing. Application July 21, 1943, Serial N0. 495,603

This invention relates to combinations of poly- 1 Claim. (Cl. zed-45.2)

vinyl acetal resins with ethers of aminotriazinealdehyde reaction products and more particularly to combinations of polyvinyl acetal resins and ethers of melamine-formaldehyde reaction products.

Polyvinyl acetal resins and "their plasti'clzed compositions have many advantageous characteristics as is known to those skilled in the art. However, the lack of form stability especially at elevated temperatures and the solubility of certain of the compositions has restricted their use to some degree. It is an object of this invention to provide improved polyvinyl acetal resin compositions. Another object is to provide polyvinyl acetal resin compositions with increased form stability. A further objectis to provide polyvinyl acetal resin compositions with increased resistance to the action of solvents.

According to the present invention, improved compositions are prepared by combining etherifled aminotriazine-aldehyde reaction products with polyvinyl acetal resins. More particularly, improved compositions are prepared by reacting etherifled amino-triazine-aldehyde reaction prod- Still more particularly, improved compositions are prepared by reacting methylol melamine ethers with polyvinyl partial acetal resins containing free hydroxyl groups.

Polyvinyl acetal resins may be prepared, for example, by hydrolyzinga, polyvinyl ester, for example, polyvinyl acetate, and then reacting the resulting hydrolysis product with an aldehyde. These resins may contain a certain proportion of ester, and hydroxyl groups in addition to the acetal groups. U. S. patent to Morrison et al Re. 20,430, dated June 20, 1937, illustrates suitable methods for preparing such resins. The polyvinyl acetal resins may be made from various "aldehydes or mixtures thereof, or even from stantially varied, but are preferably residues of saturated lower aliphatic acids such as formic acid, acetic acid, propionic acid and butyric acid.

. The degree of polymerization of the polyvinyl esters used inmaking the polyvinyl acetais, as evidenced by the viscosity of solutions thereof may be substantially varied, for example, the viscosities of 1 molar benzene solutions at 20 C. may vary from 5-75centipoises. In making the polyvinyl acetal resins from about 30 to about 95% of the ester groups are replaced by acetal groups.

According to one embodiment of this invention, i

the polyvinyl acetal resins employed contain, on a weight basis, at least 5% hydroxyl groups calculated as polyvinyl alcohol, and preferably from 5 to hydroxyl groups. These resins may also contain from 0 to 40% ester groups calculated as polyvinyl ester, the ester groups preferably being acetate.

According to one embodiment of this invention, when the acetal groups are butyraldehyde acetal, the resins employed may be considered to be made up, on a weight basis, of 12-22% hydroxyl groups calculated as polyvinyl alcohol, 15-30% acetate groups calculated as polyvinyl acetate, and the and the balance substantially butyraldehyde acetal.

According to one embodiment of this invention, when the acetal groups are acetaldehyde acetal, the polyvinyl acetal resin employed may be considered to be made up, on a weight basis, of 5 to 15% hydroxyl groups calculated as polyvinyl alcohol, 15-20% acetate groups calculated as polyvinyl acetate and the balance substantially acetaldehyde acetal.

According to one embodiment of this invention, whenthe acetal is formaldehyde acetal, the polyvinyl acetal resin may be considered to be made up, on a weight basis, of 5-10% hydroxyl groups calculated as polyvinyl alcohol, 815% acetate groups calculated as polyvinyl acetate and the balance substantially formaldehyde acetal.

An example of a mixed acetal resin is one containing on a weight basis, 13% hydroxyl groups calculated as polyvinyl alcohol, 2-6% acetate groups calculated as polyvinyl acetate and the balance 65-50 mol per cent acetaldehyde acetal and 3540 mol per cent butyraldehyde acetal.

Etherified melamine-formaldehyde reaction products may be prepared by reacting melamine, formaldehyde and an alcohol, preferably a monohydric alcohol. According to one embodiment of this invention. the others are prepared by reacting formaldehyde and melamine to produce an intermediate reaction product and the resulting product is then reacted with a monohydrlc alcohol. Melamine-formaldehyde intermediate reaction products comprise methylol derivatives of melamine or mixtures thereof and condensation products of these methylol derivatives. Thus, mono-, di-. tri-, tetra-, penta-, and hexamethylol melamines or mixtures thereof and their condensation products containing free methylol groups may be prepared and then reacted with an alcohol. The number of methylol groups formed on the melamine molecule depends primarily on the molecular ratio of formaldehyde reacted with the etherifying alcohol employed. 2-6 etherified methylol groups for each molecule of melamine are generally required. According to another embodiment the methylol melamine ethers employed are the result of substantially completely etherifying methylol melamine products containing 2-6 methylol groups.

The following is one method by which ethers of methylol melamines may be prepared. Melamine and formaldehyde are reacted in the desired molar ratio, for example, 3 mols of formaldehyde in an aqueous 37% solution for each mol of melamine, in the presence of sufiicient sodium hydroxide to produce initially a pH of 9.3 (glass electrode). The reaction is carried out with agitation at atmospheric pressure at a temperature of substantially 80-90 C. As soon as the mixture becomes clear, indicating that the melamine has reacted, the solution is diluted with an equal volume of water and allowed to cool. On cooling, a crystalline product is formed which is separated by filtration. The crystalline product is found to be substantially trimethylol melamine when a molar ratio of formaldehyde to melamine of 3:1 is

used.

The crystalline product obtained as described above is treated with ethyl alcohol in substantial excess of the amount needed to react with all of V the methylol groups present, for example, five times the theoretical amount at a temperature of about 40 C. after the addition of sufficient phosphoric acid to produce a pH of about 45. The reaction is continued until a clear solution is formed These crystals are separated by filtration and the filtrate concentrated by vacuum distillation to the desired solids content, for example, about 70% olids. This resulting product comprises essentially an alcohol paste or slurry of the ether of the methylol melamine, in this case substantially triethyl ether of trimethylol melamine.

Included within the scope of this invention are various methylol melamine ethers. According to one embodiment of this invention the ethers employed are alkyl ethers of di-, tri-, tetra-, penta-, and hexa-methylol melamine, or mixtures thereof, in which the alkyl radical contains less than 7 carbon atoms. Examples of such ethers are the di-, tri-, tetra-, pentaand hexaethyl ethers of di-, tri-, tetra-, pentaand hexamethylol melamines, respectively, tri-propyl, tri-butyl, trl-hexyl and tri-amyl ethers of tri-methylol melamine. A particular embodiment of this invention comprises the use of the ethyl ethers of tri-, tetra-, penta-, and hexamethylol melamine or mixtures thereof.

The following examples set forth certain embodiments of the present invention. Where parts are given, they are parts by weight.

The polyvinyl butyraldehyde acetal resin employed in Examples I-III and VII-XI is prepared from a polyvinyl acetate of such a degree of polymerization that a one-molar benzene solution possesses a viscosity of substantially 50-55 centipoises at 20 C. The polyvinyl butyraldehyde acetal resin may be considered to be made upon a weight basis of 16-20% hydroxyl groups calculated as polyvinyl alcohol, less than 3% acetate groups calculated as polyvinyl acetate and the balance substantially butyraldehyde acetal; The methylol melamine ethers are prepared by the method given above.

Example I Parts Polyvinyl butyraldehyde acetal resin 100 Dibutyl sebacate. 25

Tetraethyl ether of tetramethylol melamine 5 The dibutyl sebacate is thoroughly mixed with the polyvinyl acetal resin in a suitable manner, for example, by means of a Banbury mixer, and the resulting mixture is transferred to milling rolls heated to a temperature of about C. An alcohol slurry of the methylol melamine ether is then slowly added on the rolls, the solvent removed by evaporation and a uniform mix is produced. The resulting product is a transparent, homogeneous, rubbery mass capable of being dissolved in certain solvents, for ex ample,,ethanol, ethyl lactate and the like and capable. of being molded by the application of heat and pressure,

to form transparent, infusible, insoluble products.

- Thus, the product described above may be molded, for example, in a cup-shaped mold, 'by subjecting the mixture to a. temperature of 140 C. for 15 minutes under a pressure of 500 pounds per square inch, and then removed from the mold after cooling to about C. During the molding operation a thermo-setting reaction takes place with the result that a transparent, infusible product is formed which maintains its molded form at the relatively high temperature at which it is removed from the mold. Furthermore, the product does not dissolve in solvents for the polyvinylacetal resin such as ethanol or ethyl lactate.

Preferably, a suitable lubricant, for example, one part of stearic acid, is added to the mixture on the rolls to prevent sticking to the mold during the molding operation. The addition of 1 part of an antioxidant, for example p-cyclohexyl phenol or resorcinol, serves to improve the weather resistance of the resulting product.

. Example II Example I is repeated except that 2.5 parts of the methylol melamine ether are employed in place of 5 parts.

Example 111 ExampleI is repeated except that parts of the methylol melamine ether are employed in having substantially the same characteristic properties.

In contrast to the molded products made as described above in Example I, a composition consisting of 100 parts of the same polyvinyl acetal resin and parts of dibutyl sebacate when molded under the same conditions, must be cooled substantially to room temperature before removal from the molds in order to maintain the molded form. The latter molded product is completely soluble in such solvents as -methanol, ethanol, and ethyl lactate while the molded product made from the composition described in Example I swells to some extent when subjected to the action of the same solvents, but does not dissolve therein.

In further contrast to Example I, an attempt to incorporate non-etherifled tetra-methylol melamine in place of the ether derivative thereof in the same polyvinyl acetal resin composition results in an opaque product. Thus, it is seen that among the unexpected results is the compatibility of the methylol melamine ethers in polyvinyl acetal resins in contrast to the methylol melamines per se and thecontinued homogeneity and transparency of the product after conversion to the insoluble, infusible state.

As further evidence of the unexpected characteristics of the products obtainable according to this invention, comparative flow tests are carried out on the composition described in Example I before and after subjecting the composition to heat treatment. These tests are carried out by means of the Rossi-Peakes flow tester (A. S. T. M. D569-41T) at 107 C. under a pressure of 100 pounds per square inch. The following table shows the results of such tests conducted on the composition of Example I after varying heat treatments. The results are expressed in terms of inches flow in 2 minute periods.

Heat treatment Flow None minutes at 99 C. 60 minutes at 99 C. 15 minutes at 110 C.

10 minutes at 160 C aisesss sort oi. cross linking or other chemical reaction' takes place between the methylol melamine etherheat treatment. These results clearly show the eilfect of the tetra ethyl ether of tetra methylol melamine on the fusibility or plasticity of plasticized polyvinyl acetal resin and coupled with the effect on solubility, demonstrate that some and the polyvinyl acetal resin.

\ While the. present invention is not limited toany particular theory of operation, it-is believed that heat treatment of the combinations of the aminotriazine-aldehyde ethers and the polyvinyl acetal resins unexpectedly causes reaction between the ethers and the polyvinyl acetal resins, and particularly with hydroxyl groups thereof when such are present, releasing small amounts of reaction products of the groups used to etherify the amino triazine aldehyde product, with hydrogen or other residues removed from the polyvinyl acetal resin.

Example IV Parts Polyvinyl formaldehyde acetal resin Diethyl phthalate 80 Tetraethyl ether of tetra methylol melamine 10 The polyvinyl formaldehyde acetal resin usedin this example is made from polyvinyl acetate having a viscosity of 15-20 centipoises at 20 C.

in a 1 molar benzene solution and-may be considered to be made up on a weight basis of 8% hydroxyl groups calculated as polyvinyl alcohol, 12% acetate groups calculated as polyvinyl acetate and the balance substantially formaldehyde acetal. -The polyvinyl acetal resin is mixed with the plasticizer in a Banbury mixer and thereafter the tetra ethyl ether of tetra methylol meiamine in ethanol solution is mixed with the resulting plastic mass heated to a temperature of -110 C. The resulting homogeneous, transparent plastic is formed into a press cake in the well-known manner for cellulose ester plastics by pressing at a pressure of about 275 pounds per square inch and at a temperature corresponding to 40 pounds steam pressure for 20 minutes. 'The resulting press cake is cooled to about room temparature and sheets are cut therefrom in the well-known manner. The resulting sheets are clear and transparent.

While the combination of polyvinyl formalde-- In addition, the sheets are still clear and transparent after the heat treatments described above. Example V Example IV is repeatedexcept that 5 parts of tetraethvl ether of tetra, methylol melamine is employed instead of 10 parts. The press cake is baked for 20 minutes at a temperature corresponding to 40 pounds per square inch steam pressure. Sheets that are heated for 20 minutes at C. swell, but do not dissolve in ethylene dichloride.

' Example VI v Parts Polyvinyl acetaldehyde acetal resin 100 Diethyl phthalate 30 Tetra amyl ether of tetra methylol melamine- 5 The polyvinyl acetaldehyde acetal resin used in this example is made from polyvinyl acetate having a viscosity of -15 centipolses at C. in a 1 molar benzene solution and may be considered to be made up on a weight basis of 7% hydrorql groups calculated as polyvinyl alcohol, 17% acetate groups calculated as polyvinyl acetate and the balance substantially acetaldehyde acetal. Compositions produced as described in previous examples possess thermosetting properties.

The method given hereinbefore for preparing the methylol melamine others for use according to this invention may be substantially varied. For example, the melamine and formaldehyde may be reacted further before being subjected to the etherlflcation reaction. According to one embodiment, the melamine is reacted with the formaldehyde solution until a precipitate is formed when a portion of the reaction product is passed into ice water. While further reaction of the melamine and formaldehyde may take place before the methylol groups are etherifled, it is generally desirable to stop the reaction before precipitation of the melamine formaldehyde reaction product takes place. The melamine-aldehyde addition compound is preferably made under alkaline conditions in the presence of such condensin'g agents as sodium hydroxide, quaternary ammonium hydroxides such as dimethyl dibenzyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetraethanol ammonium hydroxide, ethylene diamine, ammonia and the like. According to one embodiment of this invention, the methylol compounds employed are the products of reacting 2-6 and preferably 3-6, molecular proportions of formaldehyde with each molecular proportion of melamine.

An alternative method of forming the etherified melamine-formaldehyde product comprises the use of the aqueous melamine-formaldehyde reaction product without separation of the methylol melamine crystals or condensed methylol melamine compounds. When operating in this manner, it is desirable to simultaneously dehydrate the reaction mixture, for example, by distillation, while continuously supplying the alcohol used to etherify the methylol melae.

According to another method, the aqueous melamine-formaldehyde reaction product is evaporated to dryness, preferably under reduced pressure at moderately elevated temperatures and the product obtained is then etherified as described hereinbefore.

Another method of producing etherifled methylol melamine products is to react simultaneously melamine, formaldehyde and an excess of alcohol. This procedure may be carried out by boiling the mixture under reflux conditions for several hours followed by dehydration, for example, by distillation under such conditions that an excess of the alcohol is present at all times.

In preparing others with the higher alcohols it is desirable to have present either a low boiling alcohol such as methanol or ethanol or to form first theether of the low boiling alcohol and then replace the lower alkyl group by reaction with the higher alcohol.

The foregoing methods for preparing methylol melamine products and etherlfled melamineformaldehyde products may also be used for the preparation of the amino-triazine-aldehyde products within the scope of this invention.

Regardless of the method employed for preparing the methylol melamine ethers it is generally desirable that the reaction take place under acid conditions although alkylation under neutral or alkaline conditions is not precluded.

The amount of the ethers incorporated in the polyvinyl acetal resins may be substantially varied. For certain purposes as little a 0.1% of the ether may be added to the polyvinyl acetal resin to produce beneficial results. For other purposes, the amount of the other may be increased to 20-25% or more based on the amount oi polyvinyl acetal resin used. When it is desired to prepare a composition capable of being molded under heat and pressure to produce a transparent, themoset product, from 240% of the ether'is desirable, particularly when the ether is prepared from a methylol melamine containing from 2-6 methylol groups and etheriiled with an excess of a monohydric alcohol containing less than 7 carbon atoms. The manner in which the others are incorporated into the polyvinyl acetal resins may be substantially varied. Thus, the others may be added in solution in organic solvents such as ethanol, methanol. etc., or .as a paste or therewith, or in a molten condition or in the solid state.

Preferably, the compositions ofthe invention include a plasticizer, but when advantageous the plasticizer may be omitted.

Included within the scope of this invention are ethers of aminotriazine-aldehyde reaction products in which the residues of the alcohols or othersubstances employed in preparing the ethers vary widely in their chemical structures. Thus, the residues may comprise aliphatic, aromatic, aliphatic-aromatic, aromatic-aliphatic, hydroaromatic and heterocyclic radicals. As examples of such radicals may be mentioned ethyl, propyl, butyl, amyl, phenyl, benzyl, toluyl, laryl, cetyl, allyl, stearyl, oleyl, furfuryl, cyclohexyl and the like. When the ethers are made from alcohols, monohydric or polyhydric alcohols or mixtures thereof may be employed, although monohydric alcoholsare preferred. Examples of such alcohols are methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, ethyl butanol, ethyl hexanol, lauryl alcohol, stearyl alcohol, benzyl alc hol, ethylene glycol, diethylene glycol, glycerol, sorbital, terpineol, furfiu-yl alcohol and the like.

A preferred group of others comprises alkyl ethers of methylol melamine, particularly those m which the alkyl group is one containing less than 7 carbon atoms. When desired the alkyl groups may be substituted for example, with halogen atoms. Examples of such substituted groups are mono-, di-, and tri-chloro-ethyl, -propyl, -butyl and -amyl radicals.

Included within the scope of this invention are other aldehyde-reactable aminotrlazines than melamine. Examples of other aminotriazines include substituted melamines, for example, chlorinated, alkylated, or phenylated melamines, cleaminated melamincs, for example, ammeline, ammelide and the like. Other examples of aminotriazines are 2,4,6-riethyl and trlphenyltriamino-1,3,5-trlazines, 2,4,6-trlhydrazino-l,3,5- triazinc, and the corresponding condensed triazines such as melam and melem, 2-amino- 1,3,5- triazine, 2-chloro-4,6-diamino-1,3,5-triazine, 2- phenyl-4-amino-6-hydroxyl-l,3,5-triazine and 8- methyl-2,4-diamino-1,3,5-triazine. Mixtures of aminotriazines are also included within the scope of this invention. When the particular aminotriazine employed contains less than 6 aldehydereplaceable hydrogen atoms, the upper limit of the proportion of formaldehyde employed may be Fit reduced. In general, when thermosetting prodin the scope of this invention. As examples may be mentioned aliphatic aldehydes such as acetaldehyde, propionaldehyde, butryraldehyde, heptaldehyde, hexaldehyde and furiural; unsaturated aldehydes such as acrolein, methacrolein and crotonaldehyde; arromatic aldehydes such as benzaldehyde; and mixtures of the foregoing aldehydes. from the reaction products of aminotriazines and aldehydes broadly. A particular group of aminotriazine-aldehyde addition products are those prepared from aliphatic aldehydes which may be termed alkylol-aminotriazines and particularly contemplated are those alkylol-aminotriazines in which the alkyl group contains less than 7 carbon atoms.

The compositions of the present invention set forth in the examples above may be employed for various uses and, in particular, those uses wherein the transparency and thermosetting characteristics of those products are advantageous. For example, the compositions described in the examples above may be employed in form.- ing molded products; in forming. transparent sheets, for use as tent windows and other applications wherea transparent self-supporting plastic sheet is required; as interlayers in laminated glass; for coating or cementing materials such as wood, cloth or other textiles, paper, glass sheets, glass fibers, metals, articles made from plastic materials suchas those made from synthetic resins and the like.

The following examples illustrate certain applications of the products of this invention.

Example VII- Parts Polyvinyl butyraldehyde acetal resin; 100 Dibutyl sebacate 40 Tetraethyl ether of tetramethylol melamine 10 The polyvinyl acetal resin and the dibutyl sebacate are mixed in a Banbury mixer and the resulting plastic mass transferred to Thropp rolls heated to a temperature of 80 C. Thereafter the tetraethyl ether of tetramethylol melamine is added and mixed in to give a homogeneous transparent rubbery composition. This composition is then formed into a press cake by the well-known method for cellulose ester plastics. In forming the press cake the mass is pressed at about 150 pounds per square inch and at a temperature corresponding to 40 pounds per square inch steam pressure for 30 minutes. The resulting press cake is cooled to about room temperature and skived intd sheets 0.015 inch thick.

The resulting sheets are then placed between glass sheets substantially 0.125 inch in thickness and the composite so formed is subjected to a temperature of 135 C. at a pressure of about 180 pounds per square inch for minutes, whereby the plastic interlayer is converted into its insoluble, lni'usible state and securely welds the glass sheets together into a clear transparent product. When the product is subjected to hammer blows the glass breaks but the broken particles are Thus, the ethers maybe prepared substantially retained by the plastic interlayer. In addition the product possesses good impact strength at both high and low temperatures when subjected to the well-known falling ball test;

Example VIII A web of cloth, for example duck cloth, is

coated with the homogeneous rubbery composition described in Example I in a suitable manner, for example, by calenderin at about 95 C. and thereafter the coated cloth is subjected to a temperature of about 130 C. to cause the coating to become thermoset. The product is a flexible, tough, solvent-resistant material, admirably adapted for raincoat, tent covering, and other applications involving exposure to outside condi-' tions.

Example IX A sheet of krait paper is coated and impregnated with a 20% ethanol solution of the product described in Example-I and thereafter the ethanol is removed by evaporation at about 75 C. The resulting product may then be subjected to highertemperature conditions in order to cause the plastic material to become thermoset, for example, about 125 C. The product so formed is highly flexible and resistant to the passage 0t moisture. Such a .product is useful for wrappingand like purposes where exclusion of moisture is desirable. when desired, a more dilute solution. of the product described in Example I may be employed so as to impregnate the paper without forming a continuous coating thereon. Such a treatment-has. the eflect of improving the wet strength or the paper without impairing other desirable properties.

The following example illustrates the preparation of face protective masks.

Example X Y Parts Polyvinyl butyraldehyde acetal resin 100 Buty] ricinoleatene 35 Plasticizer 8.0. 15 Stearic acid 1 Tetraeth'yl ether of tetramethylofhielamine- 5 "mold is cooled under pressure until the temperature drops to about C; The foregoing complete cycle takes about 15 minutes.

The product is a clear, insoluble, infusible, transparent, flexible, toughand substantially gasresistant productadmirably adapted for the purpose set out above or other purposes requiring similar properties. In particular, the product is free from tackiness and'retainsits shape well even at elevated temperatures.

Example XI This is an example illustrating-the use or the products of this invention for cementing purposes.

I Parts Polyvinyl butyraldehyde acetal resin Dibutyl sebacate 3'7 10 Triethyl ether of trimethylol melamine auasoe Parts Monoethyl phosphoric acid. 21 Ethanol 100 The resulting mix is a cement that becomes thermoset at room temperature and is highly advantageous for cementing articles made or or coated with thermoset polyvinyl acetal resin-phenol-aldehyde compositions.

Other accelerators may be employed in place of monoethyl phosphoric acid, for example, di-ethyl phosphoric acid, hydrochloric acid, benzene sul-- ionic acid.

Among other uses may be mentioned the preparation of emulsions, particularly aqueous emulsions, for coating purposes.

Thus, the composition of Example I may be dispersed in water by means of a colloid mill or the like in the presence or such a dispersion agent as polyvinyl alcohol. Such products may be used to coat wood, paper and the like and thereafter be cured to the insoluble state by the action of heat. When advantageous, the resin may be converted into its insoluble state after the dispersion in an aqueous or organic liquid and then used for coating purposes. Such a. dispersion is highly advantageous as a bonding material for plywood.

Products prepared according to this invention may be substituted for rubber for certain purposes. For example, the composition described in Example X may be employed in place of rubber in forming transparent tubing used, for example, in conveying blood plasma.

When desired, suitable fillers such as wood flour, carbon black, powdered mica and the like, dyestuffs, pigments and the like may be incorporated in the products of the present invention. It may be desirable to incorporate agents to accelerate the rate of hardening as for example 1-10 12 parts 0! a metal oxide such as zinc oxide, borax, salicylic acid, etc., for every 100 parts of the polyvinyl acetal resin. When it is desirable to retard the hardening rate, such materials as quaternary ammonium hydroxides are efl'ective. for example, 0.5 parts 01' trimethyi benzyl ammonium hydroxide or tetraethyl ammonium hydroxide for each 100 parts of the polyvinyl acetal resin.

- What is claimed is:

A composition of matter comprising 100 parts of a polyvinyl butyraldehyde acetal resin contain-v ing, on a weight basis, from 5-25% hydroxy groupscalculated as polyvinyl alcohol, 37 parts of dibu-tyl sebacate, 10 parts of the ethyl ether of trimethylol melamine and 1.3 parts of monoethyl phosphoric acid, said ether being incorporated while in the fusible state.

, RICHARD D. DUNLOP.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date Re. 20,430 Morrison June 29, 1937 2,197,357 Widmer et a1 Apr. 16, 1940 2,243,560 Hall et al May 2'7, 1941 2,274,447 Hodgins et al Feb. 24, 1942 2,326,698 Swain et a1. Aug. 10, 1943 2,329,622 Johnstone et al Sept. 14, 1943 2,368,451 DAlelio Jan. 30, 1945 2,396,098 Haas Mar. 5, 1946 2,423,565 Rodman July 8, 1947 OTHER REFERENCES Pages 2 and 3, Resinous Reporter, May 1943, vol. IV, No. 2, pub. by Resinous Products and Chemical Co., Philadelphia, Pa-

Pages 769, 771, 772, 778, 779, Hodgins et al., Ind. 8: Eng, Chem., June 1941.

Pages -48 and 51, Uformite, pub. Apr. 1941, by Resinous Products and Chemical 00., Philadelphia. 

